Chloroalkyl chloro-bicycloheptadienecarboxylates



United States Patent Ofiice 3,03%,114 Patented May 22, 1 962 wherein X and Y are selected from the group consisting of chlorine and hydrogen atoms and R is selected from the group consisting of a hydrogen atom, the radical CH and the radical CH CH .v These new com pounds are useful as pesticides, particularly as miticides and fungicides.

The compounds of this invention can be obtained readily, for example, by the addition of a tetrato hexachlorinated cyclopentadiene to the appropriate ester of propiolic acid. At least equimolecular proportions of the reactants should be used for this adduction reaction, but it is convenient to use an excess of the chlorinated cyclopentadiene. A solvent need not be used, but inert solvents can be used if desired. Improved yields are obtained by adding to the reaction mixture a few percent of a hydrogen chloride scavenger such as propylene oxide and a trace of a polymerization inhibitor such as hydroquinone. The reaction temperature is not critical, although reaction temperatures in the range from about normal room temperature to about 100 C. are preferred. The product which is isolated by distilling off any solvent or unreacted starting materials in vacuo is Often sufliciently pure for pesticidal use as such, but it can be purified, for example, by fractional distillation or by crystallization from a suitable solvent.

Chlorinated cyclopentadienes suitable for preparing the compounds of this invention are hexachlorocyclopentadiene (a chemical of commerce), 1,2,3,4,5-pentachlorocyclopentadiene, and 1,2,3,4-tetrachlorocyclopentadiene. The latter two compounds can be obtained for example, by the catalytic hydrogenation of hexachlorocyclopentadiene in the presence of a platinum or palladium catalyst as described by McBee and Smith, J. Am. Chem. Soc, 77, 389 (1955). When hexachlorocyclopentadiene is used as the starting material, both X and Y are chlorine atoms in the final product. When 1,2,3,4,S-pentachlorocyclopentadiene is used, one of X or Y is a chlorine atom and the other is a hydrogen atom. When l,2,3,4-tetrachlorocyclo pentadiene is used, both X and Y are hydrogen atoms.

The esters of propiolic acid also used as starting materials in the preparation of the compounds of this invention are 2-chloroethy1 propiolate, 2-chloropropyl propiolate, and 2-chlorobutyl propiolate. These esters can be prepared by the esterification of propiolic acid with the alcohols 2-chloro-1-ethano1 (ethylene chlorohydrin), 2- chloro-l-propanol, and Z-chloro-l-butanol, respectively, in the conventional manner. When 2-chloroethy1 propiolate is used as a reactant in the preparation of the compounds of this invention, R in the final product will be a hydrogen atom. When the 2-chloropropyl and 2-chlorobutyl Example 1,. namely 2 propiolates are used, R in the final product is the radical -CH and the radical CH CH respectively.

The manner in which the compounds of this invention can be prepared is illustrated in the following examples.

EXAMPLE 1 Preparation of Z-Chloroethyl 1,2,3,4,7,7-Hexachl0r0bicyclo (2.2.1 -2,5-Heptadiene-S-Carboxylate 2-chloroethy1 propiolate was prepared from ethylene chlorohydrin and propiolic acid in the presence of concentrated sulfuric acid as described by Heaton and Noller, I Am. Chem. Soc. 71, 2948-9 (1949).

Hexachlorocyclopentadiene (170 g.; 0.62 mole), 2- chloroethyl prop-iolate (38 g.; 0.29 mole), 2 ml. of propylene oxide, and a trace of hydroquinone were stirred at C. for 18 hours in a round-bottomed flask fitted with a reflux condenser, mechanical stirrer, and internal thermometer. The reaction mixture was then fractionated in vacuo to give 70 g. (60% of theory) of 2-ch1oroethyl 1,2, 3,4,7,7-hexachlorobicyclo-(2.2.1)-2,5-heptadiene 5 carboxylate, a viscous yellow oil, boiling point 144 C. under 0.3 mm. pressure, index of refraction (D line) at 24 C. of 1.5532.

Analysis for C H CI O Theory: C, 29.63%; H 1.24%; CI, 61.23%. 61.74%.

Other useful compounds within the scope of this invention can be prepared in the manner detailed in the above example. Given in the following examples are the propiolic acid ester and the chlorinated cyclopentadiene used to give the resulting compounds of this invention. For brevity, 1,2,3,4-tetrachloro-, 1,2,3,4,5-pentachloro-, and hexachlorocyclopentadiene are referred to hereinafteras A, B, and C, respectively.

EXAMPLE '2 2-chloro-1-propanol-l-C=2 chloropropyl 1,2,3,4,7,7- hexachlorobicyclo(2.2.1 -2,5-heptadiene-S-carboxylate.

H EXAMPLE 3' Ethylene chlorohydrin+A=2-chloroethyl 1,2,3,4-tetrachlorobicyclo(2.2.1 -2,5-heptadiene-5-carb oxylate.

EXAMPLE 4 2-chloro-1-propanol+A=2-chloropropyl 1,2,3,4 tetrachlorobicyclo (2.2.1 )-2,S-heptadiene-S-carboxylate.

Found: C, 28.74%; H, 1.40%; Cl,

EXAMPLE 5 2-chloro-l-butanol-l-C:2-ch1orobutyl 1,2,3,4,7,7-hexachlorobicyclo(2.2. 1 -2,5-heptadiene-5-carboxylate.

EXAMPLE 6 2 chloro -1 butanol +A=2 chlorobutyl 1,2,3,4- tetrachlorobicyc1o(2.2.1) 2,5 heptadiene 5 carboxylate.

EXAMPLE 8 2 chloro 1 propanol+B=2 chloropropyl 1,2,3,4,7- pentachlorobicyclo( 2.2.1) 2,5 -heptadiene 5 carboxylate.

EXAMPLE 9 2 chloro 1 butano1+B=2 chlorobutyl 1,2,3,4,7- pentachlorobicyclo 2.2.1 )-2,S-heptadiene-S-carboxylate.

The toxicity of the compounds of this invention as pesticides is illustrated by the toxicity of the product of chloroethyl 1,2,3,4,7,7-hexachlorobicyclo(2.2.l) 2,5 heptadiene carboxylate, to fungi. Thus, experiments were carried out in which the toxicity of candidate compounds to test spores was determined by the slide germination technique adopted by the Committee on Standardization of Fungicidal Tests of the American Phytopathological Society. Measured concentrations of spores were placed on glass slides in contact with various concentrations of the compound being tested. Percentage germination of spores was then determined for each treatment after 24 hours incubation at 72 F. 'IWo replicates were run at each concentration. The results are summarized in the following table:

1 Effective dosage for 50% control.

Experiments were also carried out for the control of bean rust on bean foliage. Pinto bean seedlings, grown under greenhouse conditions, were mounted on a special compound turntable and sprayed with the test compounds at various concentrations for 30 seconds at 30 pounds pressure. The plants were allowed to dry, inoculated with spore suspensions of the bean rust organism (Uromyces phaseoli), and placed in an incubation chamber for 24 to 48 hours. The plants were then removed and maintained under greenhouse conditions for 10 to 14 days. The number of rust pustules on the leaves of each plant was then determined. Two replicates were run at each concentration. The results obtained with the product of Example 1 are summarized as follows:

lilfiective dosage for 95% control.

This same compound has also been shown to be an effective miticide. In these experiments, the chemical was formulated as a 10 percent wettable powder and dispersed in water at a concentration of 0.1%. Cranberry bean plants infested with adults of the two-spotted spider mite (Tetranychus bimaculatus) were then dipped in this suspension. Within 72 hours after treatment, 100% mortality of the mites was observed, whereas all the mites were still alive on an untreated control.

Pesticidal compositions of this invention are prepared by mixing one or more of the new compounds of this invention with inert carriers to provide formulations adapted for ready and 'efficient application with conventional applicator equipment to the site of the pest infestation. For example, pesticidal compositions or formulations according to this invention are prepared in the form of solids or liquids; Solid compositions are preferably in the rot-m of dusts. These are prepared to give homogeneous, free-flowing dusts by admixing the active compound or compounds of this invention with finely divided solids 'suchas the tales, natural clays, pyrophy-llite, diatomaceous earth, fullers' earth, or flours such as walnut shell; wheat, redwood, soya bean, or cottonseed flours. Other inert solid arnersor the type ordinarily used in preparing pest control compositions in dusts or powdered form can also be'used.

Liquid compositions according to this invention are prepared by admixing one or more of the new compounds of this invention with a suitable inert liquid diluent. In some cases the compounds are sufficiently soluble in the common pesticide solvents such as kerosene, xylene, fuel oil, the alkylated naphthalenes, and the like so that they can be used directly as solutions in these substances. However, the pesticidal compositions of this invention can also contain a surface-active agent of the kind used in the art to enable the active compounds to be readily dispersed in water or other liquids to give sprays, which are a preferred method of applying the active compounds of this invention. The surface-active agents can be of the anionic, cationic or nonionic types. Typical examples of such surface-active agents are sodium stearate, potassium laurate, morpholine oleate, sodium lauryl sulfate, sodium Z-ethylhexyl sulfate, sodium naphthalenesulfonate, sodium alkylnaphthalenesulfonate, sodium sulfosuccinate, sodium oleic acid sulfonate, sodium castor oil sulfonate, glycerol monostearate containing a soap (or a sodium fatty alcohol sulfate), lithium stearate, magnesium oleate, aluminum stearate, methyl cellulose, sodium salt of ligninsulfonic acid, polyoxyethylene fatty alcohol ethers, polyglycol [fatty acid esters, polyoxyethylene modified fatty acid esters, polyoxyethylenepolyol fatty acid esters, polyoxypropylene fatty alcohol ethers, polypropylene glycol fatty acid esters, polyoxypropylene modified fatty acid esters, polyoxypropylene-polyol fatty acid esters, polyol fatty acid monoesters, lecithin, diand higher polyhydric alcohol fatty acid esters, cholesterol and other fatty acid esters, lanolin, oxidized fatty oils, quaternary ammonium salts such as lauryl dimethyl benzyl ammonium chloride, amine hydrochlorides such as laurylamine hydrochloride, alkylated aryl polyether alcohols such as the condensation product of diamylphenol with ethylene oxide, and the like. Mixtures of such agents can be used to combine or modify properties. The proportion of these agents will ordinarily vary from about 1% or less to about 15% by weight of the pesticidal compositions. Other pesticides as well as such sub stances as fertilizers, activators, adhesives, Spreaders, and synergists can be added to these formulations if desired. The manner in which typical pesticidal compositions according to this invention can be prepared is illustrated in the following examples. All quantities given are in parts by weight.

. EXAMPLE 10 Preparation of an Emulsifiable Concentrate The following ingredients are blended thoroughly until a homogeneous liquid concentrate is obtained. This concentrate is mixed with water to give an aqueous dispersion containing the desired concentration of active compound for use as a spray.

2-chloroethy1 1,2,3,4,7 ,7-hexach1orobicyclo 2.2.1

2,5-heptadiene-5-carboxylate 25 Sodium lauryl sulfate 2 Sodium lignin sulfonate 3 Kerosene 70 EXAMPLE 11 Preparation of q Wettable Powder The following components are mixed intimately in conventional mixing or blending equipment and are then ground to a powder having an average particle size of less than about 50 microns. The finished powder is dispersed in water to give the desired concentration of active corn-pound.

2 chloropropy-l 1,2,3 ,4,7,7-hexachlorobicyclo( 2.2.1

2,5-heptadiene-5-carboxylate 75.00 Fullers earth 22.75 Sodium lauryl sulfate 2.00 Methyl cellulose ...n .25

5 EXAMPLE 12 Preparation of an OiL-Dispersible Powder The following components are blended and ground as described in the previous example to give a powder which can be dispersed in oil to form a spray containing the desired concentration of active compound.

2-chlorobutyl 1,2,3 ,4,7,7-hexachlorobicyclo (2.2.1 -2,5-

heptadiene-5-carboxylate 70 Condensation product of diamylphenol with ethylene oxide 4 Fullers earth 26 EXAMPLE 13 Preparation a Dust The following ingredients are mixed thoroughly and then ground to an average particle size of less than about 50 microns to give a dust suitable for application with conventional dusting equipment.

2-chloroethyl l,2,3,4-tetrachlorobicyclo( 2.2.1 -2,5-

heptadiene-S-carboxylate 20 Talc 8O EXAMPLE 14 Preparation of a Granular Formulation 2-chloroethyl 1,2,3,4,7-pentachlorobicyclo(2.2. l

2,5-heptadiene--carboxylate Fullers earth 66 Dexnin Sodium lignin sulfonate 3 Kerosene 1 When the compounds and compositions of this invention are used as fungicides to control or prevent plant diseases caused by fungi or bacteria, they are used in several Ways, depending on the particular chemical, the nature of the disease, and the nature of the plant attacked. They may be used as preventive agents to form a toxic barrier between the inoculum and the host tissue, to inhibit the production of inoculum, or to destroy the inoculum before it reaches the site of infection. They may be used as eradicating agents to destroy the disease-producing organism or its inoculum on the host tissue or in the soil. They may be used as curatives or therapeutic agents to destroy the disease-producing organisms within the plant tissues, halt their growth, or inhibit the development of their toxins or counteract them. They may also be used as prophylactic agents to immunize plants against disease. The compounds of this invention can be useful in any one or more of the above ways, but since it is much easier to protect plants from disease rather than to cure disease, the chemicals are best used in the form of protectants. These protective chemicals can act to prevent sporulation and thus reduce or eliminae the inoculum necessary for the spread of a disease. They can also prevent spores from completing their germination or incubation stage so that no infection ensues. These eradicant chemicals, which can also be considered broadly as protectants, are used to destroy disease-producing organism or their inoculum in the soil, in dead plant organs, or on living plant tissue. When used to treat soil or seed, these compounds are usually referred to as disinfectants or disinfestants. The compounds of this invention are also useful for the control of fungi growth on wood, plastics, textiles, and like materials.

When used for the control of plant diseases, the compounds of this invention can be used as seed treatments, soil treatments, or plant treatments. Many of the diseaseproducing bacteria and the fungi that cause blights, spots, and rots are carried on or in seeds, roots, bulbs, tubers, corms, or other seed stock that is purchased by growers. These disease-producing organisms can be destroyed by dipping the seed or planting stock in liquid formulations of the compounds of this invention. Many plant pathogens are also soil-borne, and the application of the active compounds to the soil is one of the useful methods for control or eradication of the organisms, particularly in greenhouses, cold frames, hotbeds, and seedbeds. Both solid and liquid compositions of the compounds of this invention can be used in such soil treatments, Which are also effective for soil nematode control. Plant treatments by chemicals in the form of liquid or solid fungicidal compositions are made on growing crops or on crop residues either to prevent the appearance or spread of diseases or to destroy the disease-causing organisms already present or both. This type of treatment is essential for plant protection from air-borne pathogenes and is also useful in controlling many seedand soil-borne pathogenes that spread externally to the upper parts of plants. Such treatment includes the application of the active chemicals internally to prevent or destroy diseased conditions. The active compounds of this invention are applied by any of these methods in amounts sufficient to exert the desired pesticidal action. The amount of the active compound present in the pesticidal compositions as actually applied for destroying or preventing pest infestations varies with the type of application, the particular pests which are to be controlled, the purpose for which the treatment is made, and the like. Generally, the solid or liquid pesticidal compositions of this invention will contain from about 0.5% to about of the active compounds.

We claim: 1. A compound of the formula wherein X and Y are selected from the group consisting of chlorine and hydrogen atoms and R is selected from the group consisting of a hydrogen atom, the radical CH and the radical -CH CH 2. 2-chloroethyl 1,2,3,4,7,7 hexachlorobicyclo(2.2.l)- 2,S-heptadiene-S-carboxylate.

3. Z-chloropropyl 1,2,3,4,7,7-hexachlorobicyclo(2.2.1)- 2,5-heptadiene-5-canboxylate.

4. Z-chlorobutyl 1,2,3,4,7,7 hexachlorobicyclo(2.2.1)- 2,5-heptadiene-5-carboxylate.

5. 2-chloroethyl l,2,3,4 tetrachlorobicyclo (2.2.l)-2,5- heptadiene-S-carboxylate.

6. 2 chloroethyl l,2,3,4,7 pentachlorobicyclo (2.2.1)- 2,5-heptadiene-5-carboxylate.

References Cited in the file of this patent UNITED STATES PATENTS 2,471,790 Sowa et al May 31, 1949 2,485,389 Van Eijk Oct. 18, 1949 2,758,918 Soloway et al Aug. 14, 1956 2,771,423 Dorinson Nov. 20, 1956 2,779,701 Robitschek et al Jan. 29, 1957 2,850,523 Dazzi Sept. 2, 1958 2,899,457 Bavley et -al Aug. 11, 1959 

1. A COMPOUND OF THE FORMULA 